Development and application of novel risk indices for assessing heavy metal pollution in aquatic sediments.

This study presents the development of a new sediment individual risk index (SIRI) and sediment complex risk index (SCRI) to assess heavy metal pollution in Anzali Wetland sediments. SIRI incorporates total metal concentrations, bioavailability, and sediment quality guidelines. SCRI, derived through principal component analysis (PCA), integrates SIRI for a comprehensive risk assessment. The newly developed indices were systematically classified. Results showed varying risk levels with SIRI values of Zn, Cr, Cu, Pb, Ni, As, Cd, and Hg as 0.82, 1.32, 0.98, 0.71, 1.41, 1.37, 0.79, and 0.79, respectively. Pb, Cd, and Hg posed very low risk, Cu and Zn posed low risk, and Cr, Ni, and As posed moderate risk. SCRI yielded an index value of 1.02, indicating a moderate level of risk for the studied stations. Pearson correlation analysis validated SCRI with a highly significant and strong correlation coefficient (0.923) with metal bioavailability, serving as a risk indicator.

Capture of Singlet Oxygen Modulates Host-Guest Behavior of Coordination Cages.

The anthracene panels of two tetrahedral MII 4 L6 cages, where MII =CoII or FeII , were found to react with photogenerated singlet oxygen (1 O2 ) in a hetero-Diels-Alder reaction. ESI-MS analysis showed the cobalt(II) cages to undergo complete transformation of all anthracene panels into endoperoxides, whereas the iron(II) congeners underwent incomplete conversion. The reaction was found to be partially reversible in the case of the 1-FeII cage. The dioxygen-cage cycloadducts were found to bind a set of guest molecules more weakly than the parent cages, with affinity dropping by more than two orders of magnitude in some cases. The light-driven cycloaddition reaction between cage and 1 O2 thus served as a stimulus for guest release and reuptake.

Size and Shape Exclusion in 2D Silicon Dioxide Membranes.

2D membranes such as artificially perforated graphene are deemed to bring great advantages for molecular separation. However, there is a lack of structure-property correlations in graphene membranes as neither the atomic configurations nor the number of introduced sub-nanometer defects are known precisely. Recently, bilayer silica has emerged as an inherent 2D membrane with an unprecedentedly high areal density of well-defined pores. Mass transfer experiments with free-standing SiO2 bilayers demonstrated a strong preference for condensable fluids over inert species, and the measured membrane selectivity revealed a key role of intermolecular forces in ångstrom-scale openings. In this study, vapor permeation measurements are combined with quantitative adsorption experiments and density functional theory (DFT) calculations to get insights into the mechanism of surface-mediated transport in vitreous 2D silicon dioxide. The membranes are shown to exhibit molecular sieving performance when exposed to vaporous methanol, ethanol, isopropanol, and tert-butanol. The results are normalized to the coverage of physisorbed molecules and agree well with the calculated energy barriers.

Physical and chemical separation of Ti, rare earth elements, Fe, and Al from red mud by carbothermal reduction, magnetic separation, and leaching.

In this study, a combination of physical and chemical separation processes was used to recover the metallic components of red mud. At first, the impact of carbothermal reduction on magnetic separation of iron was studied. Low magnetic properties of iron minerals resulted in insignificant separation of iron from other components in the non-carbothermally reduced sample. Various carbothermal reduction parameters were optimized to maximize iron separation from other components. The optimum conditions were found T = 1350 °C, t = 120 min, coal/red mud ratio of 3, reaction time of 120 min, and the soda ash/red mud ratio of 0.2. Under the optimum condition, the iron recovery of the magnetic product was observed 91% with 81% Fe content, while the non-magnetic product has contained 90% of Ti and Al and 80% of rare earth elements (REEs). Following the physical separation of iron, the chemical separation of remaining red mud components was investigated using leaching with sulfuric, hydrochloric, and nitric acids. The leaching experiments were performed on two samples, treated red mud with carbothermal reduction and an untreated sample. The untreated sample had a higher dissolution efficiency for Ti and REEs than the carbothermally reduced sample. Different dissolution behavior of the red mud components was explained by samples' mineralogy. In the end, considering the obtained results, various scenarios for the recovery of red mud components were evaluated from technical and environmental aspects.

Trap Inlaid Cationic Hybrid Composite Material for Efficient Segregation of Toxic Chemicals from Water.

Metal-based oxoanions are potentially toxic pollutants that can cause serious water pollution. Therefore, the segregation of such species has recently received significant research attention. Even though several adsorbents have been employed for effective management of chemicals, their limited microporous nature along with non-monolithic applicability has thwarted their large-scale real-time application. Herein, we developed a unique anion exchangeable hybrid composite aerogel material (IPcomp-6), integrating a stable cationic metal-organic polyhedron with a hierarchically porous metal-organic gel. The composite scavenger demonstrated a highly selective and very fast segregation efficiency for various hazardous oxoanions such as, HAsO42- , SeO42- , ReO4- , CrO42- , MnO4- , in water, in the presence of 100-fold excess of other coexisting anions. The material was able to selectively eliminate trace HAsO42- even at low concentration to well below the AsV limit in drinking water defined by WHO.

Analytical Methods for the Determination of 90Sr and 239,240Pu in Environmental Samples.

Artificial long-lived radionuclides such as 90Sr and 239,240Pu have been long released into the environment by human nuclear activities, which have a profound impact on the ecological environment. It is of great significance to monitor the concentration of these radionuclides for environmental safety. This paper summarizes and critically discusses the separation and measurement methods for ultra-trace determination of 90Sr, 239Pu, and 240Pu in the environment. After selecting the measurement method, it is necessary to consider the decontamination of the interference from matrix elements and the key elements, and this involves the choice of the separation method. Measurement methods include both radiometric methods and non-radiometric methods. Radiometric methods, including alpha spectroscopy, liquid scintillation spectrometry, etc., are commonly used methods for measuring 239+240Pu and 90Sr. Mass spectrometry, as the representative of non-radiometric measurement methods, has been regarded as the most promising analytical method due to its high absolute sensitivity, low detection limit, and relatively short sample-analysis time. Through the comparison of various measurement methods, the future development trend of radionuclide measurement is prospected in this review. The fully automatic and rapid analysis method is a highlight. The new mass spectrometer with ultra-high sensitivity shows strong analytical capabilities for extremely low concentrations of 90Sr, 239Pu, and 240Pu, and it is expected to develop determination methods with higher sensitivity and lower detection limit.

Mass Transfer in Boronate Ester 2D COF Single Crystals.

Unlike graphene and similar structures, 2D covalent organic frameworks (2D COFs) exhibit intrinsic porosity with a high areal density of well-defined and uniform openings. Given the pore size adjustability, 2D COFs are likely to outperform artificially perforated inorganic layers with respect to their prospects in membrane separation. Yet, exploring the mass transport in 2D COFs is hidden by the lack of laterally extended free-standing membranes. This work reports on direct molecular permeation measurements with single crystals of an interfacially synthesized boronate ester 2D COF. In accordance with the material topography, the atmospheric and noble gases readily pass the suspended nanosheets while their areal porosity is quantified to be almost 40% exceeding that in any 2D membranes known. However, bulkier aromatic hydrocarbons are found to deviate substantially from Graham's law of diffusion. Counterintuitively, the permeation rate is demonstrated to rise from benzene to toluene and further to xylene despite the increase in the molecular mass and dimensions. The results are interpreted in terms of adsorption-mediated flow that appears to be an important transport mechanism for microporous planar nanomaterials.

Zirconium Metal-Organic Frameworks Integrating Chloride Ions for Ammonia Capture and/or Chemical Separation.

Ammonia capture by porous materials is relevant to protection of humans from chemical threats, while ammonia separation may be relevant to its isolation and use following generation by emerging electrochemical schemes. Our previous work described both reversible and irreversible interactions of ammonia with the metal-organic framework (MOF) material, NU-1000, following thermal treatment at either 120 or 300 °C. In the present work, we have examined NU-1000-Cl, a variant that features a modified node structure-at ambient temperature, Zr6(µ3-O)4(µ3-OH)4(H2O)812+ in place of Zr6(µ3-O)4(µ3-OH)4(OH)4(H2O)48+. Carboxylate termini from each of eight linkers balance the 8+ charge of the parent node, while four chloride ions, attached only by hydrogen bonding, complete the charge balance for the 12+ version. We find that both reversible and irreversible uptake of ammonia are enhanced for NU-1000-Cl, relative to the chloride-free version. Two irreversible interactions were observed via in situ diffuse-reflectance infrared Fourier-transform spectroscopy: coordination of NH3 at open Zr sites generated during thermal pretreatment and formation of NH4+ by proton transfer from node aqua ligands. The irreversibility of the latter appears to be facilitated by the presence chloride ions, as NH4+ formation occurs reversibly with chloride-free NU-1000. At room temperature, chemically reversible (and irreversible) interactions between ammonia and NU-1000-Cl result in separation of NH3 from N2 when gas mixtures are examined with breakthrough instrumentation, as evinced by a much longer breakthrough time (∼9 min) for NH3.

Cyclotron production of no carrier added 186gRe radionuclide for theranostic applications.

186gRe (T1/2 = 3.7183 d, E(ß-)mean = 346.7 keV, I(ß-)mean = 92.59%), a mixed beta and γ-emitter shows great potential for use in theranostic applications. The dominant 185Re(n,γ) route, via use of a nuclear reactor, provides 186gRe in carrier added form with low specific activity, while cyclotrons offer no carrier-added (NCA) high specific activity production of 186gRe. However, to be able to select the best possible nuclear reaction and to optimize the production route via the use of a cyclotron, information on the excitation function for the reaction of interest as well as for the competing reactions is necessary. Accordingly, we have conducted a detailed study of the excitation functions for natW(d, x) reactions in seeking optimized parameters for the NCA production of 186gRe. Noting a discrepancy among the experimental data, we made an evaluation of the available literature, finally selecting optimum parameters for the production of 186gRe via the 186W(d,2n)186Re reaction. These beam parameters were then used for batch production of 186gRe by irradiating an enriched 186W metallic powder target, followed by a subsequent automated chemical separation process. The preliminary results show 98.1% radionuclidic purity of 186gRe at 8 h subsequent to the End of Bombardment (EOB), offering the potential for use in clinical applications.

Development of 'on-site' measurement methods for assay of plutonium isotopes.

Over the past decades, radioanalytical methods for environmental monitoring of plutonium (Pu) isotopes from contaminated soils were developed to respond in case of a nuclear accident but also for routine analyses. In this paper we prove the possibility of on-site analysis of plutonium using alpha particle spectrometry. Tests are performed with two types of soils: a "brown" soil and a "sandy" soil, both spiked with 242Pu. The proposed method starts with leaching the soil, then separating the radionuclides of interest through a TEVA column and finally preparing counting planchets for alpha-spectrometry analyses. The aim of this work was to obtain a fast and reliable procedure, from the sample preparation to the analysis, applicable directly in the field and lasting no longer than a working day. The testing involved several parameters, such as the soil-to-liquid ratio, the acid molarity, the influence of a purification step, the source preparation. For each procedure defined, the time and the recovery rates of 242Pu were recorded and compared. Results have proven that the recovery rates increase with the solid-to-liquid ratio, with the acid molarity, with the purification step but decrease with the mixing time. The two methods used for source preparation showed similar results and the sources were measured by alpha spectrometry, using two different counting devices. The final selected sample preparation procedure has a throughput of 3 h, with recovery rates of 33.8 ± 3.1% for the "brown" soil and 77.3 ± 9.2% for the "sandy" soil and is suitable for a field application.

A coherent method for combined stable magnesium and radiogenic strontium isotope analyses in carbonates (with application to geological reference materials SARM 40, SARM 43, SRM 88A, SRM 1B).

We undertook 87Sr/86Sr analyses for a range of carbonate bearing geological reference materials, and combined these with δ26Mg for a subset of samples. Following chemical purification in a series of chromatographic extractions, isotope ratios were measured by Multi-Collector-ICP-MS using a Plasma II (Nu instruments, Wrexham, UK). To validate efficient sample digestion procedures of carbonate fractions, total samples were treated with either 3 mol l-1 HNO3 and 0.5 mol l-1 HCl, respectively. Results of both leaching procedures are identical within reproducibility. Reference values for SRM 88A (formerly NBS 88A), SRM 1B (formerly NBS 1B), SARM 40, SARM 43, JDo-1, JLs-1, and San Carlos olivine range from 0.70292 to 0.73724 in 87Sr/86Sr and from -2.80 to -0.41 ‰ for δ26Mg, respectively. This set of geological reference materials can be used for sedimentary rock material with different carbonate mineral and matrix composition as quality control measurements of combined stable Mg and radiogenic Sr isotope analyses.•We present a protocol that facilitates the chemical separation of Mg and Sr in carbonate bearing geological reference materials including 87Sr/86Sr and δ26Mg of certified reference materials.

165Er: A new candidate for Auger electron therapy and its possible cyclotron production from natural holmium targets.

165Er, a pure Auger-electron emitter, could be an attractive candidate for targeted radionuclide therapy. Auger electrons possess short penetration paths with high linear energy transfer. In this study, experimental cross-sections of the 165Ho(p, n)165Er nuclear reaction were measured and targets irradiated with protons using Injector II cyclotron at Paul Scherrer Institute (Switzerland) and the 18 MeV medical cyclotron laboratory at the University Hospital in Bern. A purification method was developed in order to obtain 165Er suitable for in vivo applications.

Quantification of Tl (I) and Tl (III) based on microcolumn separation through ICP-MS in river sediment pore water.

Thallium (Tl) is a typical toxic element, whose biological effects and geochemical behavior are closely related with its chemical speciation in the environment. In this context, the objective of the present study was to develope an effective method for separation of Tl (I) and Tl (III) based on solid-phase extraction (SPE) using anion exchange resin AG1-X8 as a sorbent and ICP-MS measurement. In this proposed method, Tl (I) and Tl (III) could be separated by selective adsorption of Tl (III)-DTPA in the resin, while Tl (III) was eluted by the solution mixed with HCl and SO2. The validity of this method was confirmed by assays of standard solutions of Tl (I) and Tl (III), as well as with spike of contaminated samples. The present study results revealed that higher concentration of Tl (I) (245.48 µg/l) and Tl (III) (20.92 µg/l) had been found near the acid mine drainage (AMD) sample of sediment pore water. The results revealed that Tl (I) of 61.47 µg/l and Tl (III) of 9.73 µg/l were present in the river water contaminated by acid mine drainage. This thallium speciation analysis implied that the dominant Tl (I) species in the river water studied might be due to the weathering of sulfide mineral-bearing rocks, mining, and smelting activities in the studied area.

Development of a separation framework for effects-based targeted and non-targeted toxicological screening of water and wastewater.

An environmental water sample fractionation framework was developed based on effects-directed analysis (EDA) to detect known and unknown compounds of concern in different waters. Secondary effluent from a wastewater treatment plant was used to demonstrate the effectiveness of the developed framework for characterizing estrogenic compounds in the effluent. The effluent was spiked with known estrogenic compounds to validate the framework in a targeted approach and an unspiked sample was also investigated in a non-targeted approach. The framework separated compounds based on polarity and adsorption using liquid-liquid extraction followed by solid phase extraction. The targeted and non-targeted effluents generated six fractions each, which were assessed for estrogenic activity using an in vitro bioassay (yeast estrogen screen - YES). Three out of the six fractions in each case, along with the raw effluent, showed estrogen equivalent concentrations (EEQs) ranging between 1.0 and 3.0 µg/L. Directed by the assay results, these estrogenic fractions were further analyzed using liquid- and gas-chromatography coupled with mass spectrometry for compound identification. The developed separation framework coupled with a bioassay aided in identification of both known and unknown compounds producing estrogenic effects in the water sample. The approach of fractionation followed by concentration helped isolate and elevate contaminant levels without necessarily concentrating potential matrix effects that could cause interfering cytotoxicity and inhibition in the bioassay. The targeted analysis showed consistency between predicted and observed results, while the non-targeted analysis revealed the presence of three estrogenic compounds in the unspiked effluent: di-isobutyl phthalate, diethyl phthalate and benzophenone, that were confirmed with standards. The study mainly aimed at development and validation of a simple yet effective EDA framework with low cost techniques for water and wastewater toxicity screening and evaluation, and the results suggested that the developed framework could be used as a screening tool for isolating and identifying unknown compounds in a complex water sample.

Precise analysis of the concentrations and isotopic compositions of molybdenum and tungsten in geochemical reference materials.

Molybdenum (Mo) is a redox-sensitive element and its concentrations and stable isotope compositions are widely used as a redox proxy in paleoceanography. Tungsten (W) is an emerging new isotope proxy, which has potential as a tracer for hydrothermal and early diagenetic processes. We present a new method for the precise and accurate analysis of Mo and W concentrations and isotope compositions from one single sample aliquot, thus saving mass of a sample and making the results directly comparable without concerns related to analytical or natural sample heterogeneity. After acid digestion, Mo and W are separated from the sample matrix using chelating resin NOBIAS Chelate-PA1 and anion exchange resin AG1 X8. Matrix removal is highly efficient: the remaining percentage is 10-2 to 10-5% with respect to the initial weight. Subsequently, samples are measured for Mo and W concentrations and isotope compositions using multi-collector inductivity coupled plasma mass spectrometry (MC-ICP-MS). For mass bias correction and determination of concentrations, we use standard-sample bracketing and in addition an external correction method employing ruthenium (Ru) for Mo and rhenium (Re) for W. This double correction approach results in an external reproducibility of or below 0.10‰ (2SD) for δ98Mo and 0.05‰ for δ186W based on ICP standard solutions (NIST SRM 3134 lot No. 130418 for Mo and NIST SRM 3163 lot No. 080331 for W). We present data for Mo and W in 12 geological reference materials including igneous rocks, sedimentary rocks, marine sediments, and manganese nodules. For Mo our method reproduces published values for the geological standard materials within analytical error of published values. For W, although published data do not always agree for a given geological standard material, our data agree within error with more recent data. We interpret a cause of the deviations is due to unknown effects of a desolvating nebulizer for MC-ICP-MS.

Production assessment of non-carrier-added 199Au by (n,γ) reaction.

Gold-199 is a promising theranostic radionuclide for targeted radioimmunotherapy as well as for scintigraphy and dosimetry. 199Au can be produced in two methods in the direct and indirect routes of the reactor production via 197Au(n,γ)198Au(n,γ)199Au as the direct or 198Pt(n,γ)199Pt→199Au as the indirect method. This investigation described the development of a method for the reactor production of no-carrier-added (NCA) 199Au through neutron activation of natural Pt in Tehran Research Reactor (TRR) at a thermal neutron flux of 3.5 × 1013 n cm-2 s-1. Also, in this paper, the activity of 199Au has been estimated using the MCNPX code. In this case, first, the reactor core is simulated. Then the calculated results are compared with the corresponding experimental values. Moreover, two different chemical separation methods are investigated experimentally in details.

Embedding and Positioning of Two FeII4 L4 Cages in Supramolecular Tripeptide Gels for Selective Chemical Segregation.

An unreported d,l-tripeptide self-assembled into gels that embedded FeII4 L4 metal-organic cages to form materials that were characterized by TEM, EDX, Raman spectroscopy, rheometry, UV/Vis and NMR spectroscopy, and circular dichroism. The cage type and concentration modulated gel viscoelasticity, and thus the diffusion rate of molecular guests through the nanostructured matrix, as gauged by 19 F and 1 H NMR spectroscopy. When two different cages were added to spatially separated gel layers, the gel-cage composite material enabled the spatial segregation of a mixture of guests that diffused into the gel. Each cage selectively encapsulated its preferred guest during diffusion. We thus present a new strategy for using nested supramolecular interactions to enable the separation of small molecules.

Designing hybrid materials with multifunctional interfaces for wound dressing, electrocatalysis, and chemical separation.

An infinite number of possibilities can emerge from the combination of phases in hybrid systems. Interfacing phases is a strategy to obtain a set of properties in one system that are beyond the abilities of single phases. Herein, the progress in materials science exploring hybrid systems are discussed from the point of view of three important applications: wound dressing; electrocatalysis; and chemical separation. These three unrelated applications exemplify the broad impact of hybrid materials, which can be coherently designed to achieve outstanding performance. Many inspiring works have been published in the last few years, remodeling the edges of human knowledge on hybrid materials. However, the challenges in the coherent design seem to rely on the development of synthetic processes to achieve stronger integration among the phases in a hybrid material.

Real-time Simutaneous Separation and Detection of Chemicals using Integrated Micro Column and Surface Plasmon Resonance Imaging Micro-GC.

An integrated and miniaturized Micro-Gas Chromatography with real-time imaging capability for simultaneous chemical separation and detection was developed. Surface Plasmon Resonance imaging (SPRi) was used as a sensitive and real-time imaging based detector for various gaseous chemical mixtures and good gas chromatographs were obtained. The system integrated a home-made miniaturized molecular sieve packed spiral micro-channel column with the SPRi imaging chip and real-time chemical separation and detection were demonstrated using alkanes. The chemical separation processes were simulated using COMSOL and matched well with experimental results. The system enabled the study of chemical separation processes in real-time by miniaturizing and integrating the Micro-GC separation and detection units. This approach can be expanded to multidimensional GC development.

Host-guest interaction of styrene and ethylbenzene in MIL-53 studied by solid-state NMR.

Solid-state NMR was utilized to explore the host-guest interaction between adsorbate and adsorbent at atomic level to understand the separation mechanism of styrene (St) and ethylbenzene (EB) in MIL-53(Al). 13C-27Al double-resonance NMR experiments revealed that the host-guest interaction between St and MIL-53 was much stronger than that of EB adsorption. In addition, 13C DIPSHIFT experiments suggested that the adsorbed St was less mobile than EB confined inside the MIL-53 pore. Furthermore, the host-guest interaction model between St, EB and MIL-53 was established on the basis of the spatial proximities information extracted from 2D 1H-1H homo-nuclear correlation NMR experiments. According to the experimental observation from solid-state NMR, it was found that the presence of π-π interaction between St and MIL-53 resulted in the stronger host-guest interaction and less mobility of St. This work provides direct experimental evidence for understanding the separation mechanism of St and EB using MIL-53 as an adsorbent.